CN105324438A - Light-resistance improver - Google Patents
Light-resistance improver Download PDFInfo
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- CN105324438A CN105324438A CN201380075704.9A CN201380075704A CN105324438A CN 105324438 A CN105324438 A CN 105324438A CN 201380075704 A CN201380075704 A CN 201380075704A CN 105324438 A CN105324438 A CN 105324438A
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- tetrafluoroethylene
- light fastness
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
- C08G2650/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group containing ketone groups, e.g. polyarylethylketones, PEEK or PEK
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Abstract
Provided is an additive with which the light resistance of a non-fluorine-based thermoplastic resin (e.g. a super engineering plastic such as an aromatic polyamide, a liquid crystal polyester, or an aromatic polyether ketone resin) can be improved or ameliorated. This additive is configured from a fluorine-containing resin. The fluorine-containing resin may include, as a polymerization component, tetrafluoroethylene or the like, and may specifically be a tetrafluoroethylene copolymer (e.g. at least one selected from a copolymer of tetrafluoroethylene and another fluorinated olefin, a copolymer of tetrafluoroethylene and a fluorinated vinyl ether, and a copolymer of tetrafluoroethylene, another fluorinated olefin, and a fluorinated vinyl ether).
Description
Technical field
The present invention relates to the additive (or modifying agent) of the photostabilization (or light stability) that can improve or improve fluorine-free thermoplastic resin (such as, the superengineering plastics such as aromatic poly amide, liquid crystal polyester, aromatic-polyether ketone resin).
Background technology
The superengineering plastics such as known aromatic poly amide, liquid crystal polyester, aromatic-polyether ketone resin (polyaryl ether ketone resin), are very excellent thermoplastic resins, but there is the situation of photostabilization deficiency in thermotolerance, physical strength etc.Such as, carry out the environment acted at light under, find that the situation of various resin properties generation rotten (such as, the reduction, variable color etc. of mechanical characteristics) is more.
As improving so sunproof method, have studied schemes such as adding general stablizer (photostabilizer, antioxidant etc.), but there is following situation: because the fusing point of superengineering plastics, mold temperature (forming process temperature) are very high, therefore in the process of forming process, stablizer general like this can carry out thermolysis, and can not be fully improved sunproof effect.In addition, not only thermolysis occurs, the resolvent of stablizer also can cause resin thickening, and thermostability is reduced.
It should be noted that, following resin combination is disclosed: it contains (A) gathers aryl ketones resin 70 ~ 99 quality % and (B) fluoro-resin 30 ~ 1 quality %, and the median size of (B) fluoro-resin disperseed in resin combination is 0.1 ~ 30 μm in Japanese Unexamined Patent Publication 2006-274073 publication (patent documentation 1).And, describe the resin-formed body that such resin combination is provided in sliding, solvent resistance, thermotolerance aspect excellence in the document.
In addition, following resin combination is disclosed: for the object improving sliding and shock resistance in WO2012/005133 publication (patent documentation 2), this resin combination comprises aromatic-polyether ketone resin and fluoro-resin, fluoro-resin is the multipolymer of tetrafluoroethylene and perfluor alefinically unsaturated compounds, the mass ratio of aromatic-polyether ketone resin and fluoro-resin is 95:5 ~ 50:50, fluoro-resin is separated into particle shape in aromatic-polyether ketone resin, and the average mark shot footpath of fluoro-resin is less than 3 μm.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2006-274073 publication (claims, [0005] section)
Patent documentation 2:WO2012/005133 publication (claims, embodiment)
Summary of the invention
The problem that invention will solve
Therefore, the object of the present invention is to provide the additive of the photostabilization (or light stability) that can improve or improve fluorine-free thermoplastic resin (particularly, superengineering plastics).
Other object of the present invention is, even if provide in the melting mixing process under high temperature, also can keep the additive of photostabilization improvement result.
The method of dealing with problems
Known technology fluoro-resin is dispersed in aromatic-polyether ketone resin as above-mentioned patent documentation, but its object is to improve sliding etc.It should be noted that, although [0049] Duan Zhongyou of patent documentation 2 is about the record of the purport had excellent weather resistance, only describe the usual characteristic as fluoro-resin, in addition, weathering resistance and photostabilization are different concepts.
Under these circumstances, the present inventor conducts in-depth research to achieve these goals, found that: unexpectedly fluorine resin can give fluorine-free thermoplastic resin (such as, superengineering plastics) improve sunproof effect, particularly to add the form of the resin combination in fluorine-free thermoplastic resin to, even if the melting mixing process then under high temperature, also do not damage thermostability etc., keep sufficient photostabilization improvement result, thus complete the present invention.
Namely, light fastness enhancer of the present invention (photostabilization activator, photostabilization imparting agent, photostabilizer), for the additive of the photostabilization (or light stability) for improving (or improvement) fluorine-free thermoplastic resin, it comprises fluorine resin.
Fluorine resin can be take tetrafluoroethylene as the fluorine resin of polymeric composition.In addition, fluorine resin also can be the thermoplastic fluorocarbon resin fluoro-resin of heat fusing (or can).The fluorine resin of representative, it can be TFE copolymer, can be especially be selected from tetrafluoroethylene and other fluorinated olefin multipolymer (such as, the multipolymer of tetrafluoroethylene and other perfluoroolefine), the multipolymer of tetrafluoroethylene and fluorinated vinyl ether (such as, the multipolymer of tetrafluoroethylene and perfluor (alkyl vinyl ether)) and tetrafluoroethylene and other fluorinated olefin and fluorinated vinyl ether multipolymer (such as, the multipolymer of tetrafluoroethylene and other perfluoroolefine and perfluor (alkyl vinyl ether)) at least a kind.
Fluorine-free thermoplastic resin, can be superengineering plastics (such as, the superengineering plastics that second-order transition temperature is more than 100 DEG C), can be selected from aromatic poly amide, liquid crystal polyester and aromatic-polyether ketone resin at least a kind [such as especially, aromatic-polyether ketone resin (such as, polyether-ether-ketone)].
Also comprise the resin combination comprising fluorine-free thermoplastic resin and above-mentioned light fastness enhancer (fluorine resin) in the present invention.In addition in the present invention, also comprise the formed body formed by such resin combination.
Further, also comprise in the present invention and above-mentioned light fastness enhancer (fluorine resin) is added (or mixing) to fluorine-free thermoplastic resin, and improve the method for the photostabilization (or light stability) of (or improvement) fluorine-free thermoplastic resin.
The effect of invention
According to additive of the present invention, can improve or improve the photostabilization of fluorine-free thermoplastic resin.And, even if such additive is through the melting mixing process of high temperature, does not cause yet and decompose or with the thickening of decomposing, therefore can keep improving or improving sunproof effect.Therefore, particularly additive of the present invention preferably goes for needing in non-fluorine-containing thermoplastic resin the thermoplastic resin of the shaping or processing under high temperature, such as, and the superengineering plastics such as aromatic poly amide, liquid crystal polyester, aromatic-polyether ketone.
In addition, because additive of the present invention is arborescens, the resin properties of fluorine-free thermoplastic resin therefore can be suppressed to reduce, also according to resin properties, fluorine-free thermoplastic resin can be given by the characteristic being derived from the excellence of fluorine resin.And, can suppress at a high level to ooze out (ブ リ ー De) etc.Therefore, with regard to additive of the present invention, validity and practicality are very high.
Embodiment
Additive of the present invention (light fastness enhancer, photostabilization activator, photostabilization imparting agent) is the sunproof additive for improving or improve fluorine-free thermoplastic resin, and it comprises: fluorine resin.
[fluorine resin]
As fluorine resin (fluoro-resin) as long as fluorine-containing (or fluorine replace) resin, be not particularly limited, can enumerate such as: using the resin (polymkeric substance) of fluorochemical monomer as polymeric composition.
As concrete using the resin (fluorine resin) of fluorochemical monomer as polymeric composition, can enumerate: the multipolymer etc. of the homopolymer of fluorochemical monomer or multipolymer, fluorochemical monomer and co-polymerized monomer.
As fluorochemical monomer, can enumerate such as, fluorinated olefin [or Fluorine containing olefine or fluorine substituted olefins, such as, vinyl fluoride, vinylidene, tetrafluoroethylene, trifluorochloroethylene, R 1216 etc. are fluoridized chain olefin and (such as, are fluoridized C
2-6alkene, preferably fluoridizes C
2-4alkene, more preferably perfluor C
2-4alkene) etc.], fluorinated vinyl ether [or fluorine-containing vinyl ether or fluorine substituted ethylene base ether, such as, the fluorinated alkyl vinyl ethers such as perfluor (methylvinylether), perfluor (ethyl vinyl ether), perfluor (propyl vinyl ether) (such as, fluoridize C
1-6alkyl vinyl ether, preferably fluoridizes C
1-4alkyl vinyl ether, more preferably perfluor C
1-4alkyl vinyl ether) etc.], [or fluorine-containing allyl ethers or fluorine substituted allyl ether, such as, the fluorinated alkyl allyl etherss such as perfluor (polyoxyethylene base ether) (such as, fluoridize C to fluorinated allyl ethers
1-6polyoxyethylene base ether, preferably fluoridizes C
1-4polyoxyethylene base ether, more preferably perfluor C
1-4polyoxyethylene base ether) etc.], fluorine-containing dioxole class monomer [such as, 2,2-bis-(trifluoromethyl)-4,5-bis-fluoro-1,3-dioxole etc.] etc.
Fluorochemical monomer can be two or more alone or in combination.
In these fluorochemical monomers, perfluorinated monomers preference is as, perfluoroolefine (such as, the perfluor such as tetrafluoroethylene, R 1216 C
2-4alkene), the perfluor (C such as perfluoroalkyl vinyl ether [such as, perfluor (propyl ethylene base) ether)
1-6alkyl vinyl ether) etc.] etc.
Therefore, fluorochemical monomer also can comprise perfluorinated monomers.Under such circumstances, whole relative to fluorochemical monomer, the ratio of perfluorinated monomers can from more than 10 % by weight (such as, more than 20 % by weight) scope is selected, such as, more than 30 % by weight (such as, more than 40 % by weight), be preferably more than 50 % by weight (such as, more than 60 % by weight), more preferably more than 70 % by weight (such as, more than 75 % by weight), can be more than 80 % by weight (such as, more than 90 % by weight) especially.
As co-polymerized monomer (other co-polymerized monomer, not fluorine-containing co-polymerized monomer), as long as can copolymerization, be not particularly limited, can enumerate such as, alkene [such as, the chain olefin such as ethene, propylene (such as, C
2-6alkene, is preferably C
2-4alkene)], halogenated olefins (such as, chlorination or the bromination C such as vinylchlorid, bromine ethene beyond fluorine
2-4alkene) etc.Co-polymerized monomer can be two or more alone or in combination.
It should be noted that, in the multipolymer of fluorochemical monomer and co-polymerized monomer, co-polymerized monomer relative to the ratio of fluorochemical monomer 100 weight part can be such as below 30 weight parts (such as, 0.01 ~ 30 weight part), be preferably below 20 weight parts (such as, 0.03 ~ 15 weight part), more preferably (such as, 0.05 ~ 5 weight part) below 10 weight parts.
The fluorine resin of representative, poly-fluorinated olefin can be enumerated (such as, tetrafluoroethylene etc.), fluorinated olefin copolymers { such as, the multipolymer of fluorinated olefin [such as, (particularly perfluoroolefine is preferably perfluor C for the tetrafluoroethylene such as the multipolymer of tetrafluoroethylene and R 1216 and other fluorinated olefin
3-4alkene) multipolymer], the multipolymer of fluorinated olefin and fluorinated vinyl ether [such as, (particularly perfluor (alkyl vinyl ether) is preferably perfluor (C for the tetrafluoroethylene such as the multipolymer of tetrafluoroethylene and perfluor (propyl vinyl ether) and fluorinated vinyl ether
1-6alkyl vinyl ether)) multipolymer; (particularly perfluoroolefine is preferably perfluor C for the tetrafluoroethylene such as the multipolymer of tetrafluoroethylene and R 1216 and perfluor (propyl vinyl ether) and other fluorinated olefin
3-4alkene) and fluorinated vinyl ether (particularly perfluor (alkyl vinyl ether), preferably perfluor (C
1-6alkyl vinyl ether)) multipolymer etc.] etc.
Wherein, with regard to using tetrafluoroethylene with regard to the fluorine resin of polymeric composition, preference is as tetrafluoroethylene; (particularly perfluoroolefine is preferably perfluor C for tetrafluoroethylene and other fluorinated olefin
3-4alkene) multipolymer; (particularly perfluor (alkyl vinyl ether) is preferably perfluor (C for tetrafluoroethylene and fluorinated vinyl ether
1-6alkyl vinyl ether)) multipolymer; (particularly perfluoroolefine is preferably perfluor C for tetrafluoroethylene and other fluorinated olefin
3-4alkene) and fluorinated vinyl ether (particularly perfluor (alkyl vinyl ether), preferably perfluor (C
1-6alkyl vinyl ether)) multipolymer; Etc..
In addition, in fluorine resin, preferably also comprise the thermoplastic fluorine-containing resin fluoro-resin of heat fusing (or can).It should be noted that, in such thermoplastic fluorocarbon resin, do not comprise tetrafluoroethylene.Due in fluorine-free thermoplastic resin, thermoplastic fluorine-containing resin is easy to carry out disperseing (differential falls apart) with smaller particle diameter, therefore can give (or finding expression in) fluorine-free thermoplastic resin well by the sunproof functioning efficiency of raising.
From the viewpoint, particularly preferably comprise TFE copolymer in fluorine resin, such as, the multipolymer etc. of the multipolymer of the multipolymer of tetrafluoroethylene and other fluorinated olefin, tetrafluoroethylene and fluorinated vinyl ether, tetrafluoroethylene and other fluorinated olefin and fluorinated vinyl ether.
It should be noted that, in TFE copolymer, the ratio of tetrafluoroethylene whole relative to TFE copolymer (or tetrafluoroethylene and be not the total amount of monomer of tetrafluoroethylene) can from more than 30 % by weight (such as, 40 ~ 99.9 % by weight) scope is selected, can be such as more than 50 % by weight (such as, 55 ~ 99.5 % by weight), be preferably more than 60 % by weight (such as, 65 ~ 99 % by weight), more preferably more than 70 % by weight (such as, 75 ~ 98 % by weight), particularly more than 80 % by weight (such as, 85 ~ 95 % by weight).
It should be noted that, fluorine resin can also through the resin of surface treatment (such as, Cement Composite Treated by Plasma, fluorine gas process, ammonia treatment etc.).
When fluorine resin has fusing point, its fusing point is not particularly limited, such as, can be less than 400 DEG C (such as, 200 ~ 380 DEG C), is preferably 230 ~ 350 DEG C (such as, 250 ~ 300 DEG C) left and right.In addition, fluorine resin also can be the resin of the melt temperature meeting melting at fluorine-free thermoplastic resin described later.
[light fastness enhancer and resin combination]
Light fastness enhancer of the present invention (fluorine resin) can be used as the sunproof additive improving or improve fluorine-free thermoplastic resin.
As fluorine-free thermoplastic resin, (not fluorine-containing thermoplastic resin, is called for short thermoplastic resin, resin etc.), as long as not fluorine-containing resin (not belonging to the resin of fluorine resin category), be not particularly limited, can enumerate such as, the halogen-containing resin of fluorine-free (such as, polyvinyl chloride, the chlorine-containing resins such as polyvinylidene dichloride), styrene resin (such as, polystyrene, the styrol copolymers such as AS resin), acrylic resin (such as, polymethylmethacrylate etc.), olefin resin [such as, chain olefin resin (polyethylene, polypropylene, polymethylpentene etc.), cyclic olefin resin (so-called COP, COC etc.) etc.], polyacetal resin, polycarbonate resin (such as, aromatic polycarbonate etc.), vibrin [such as, aliphatic polyester resin (such as, poly(lactic acid) etc.), aromatic polyester resin (polyarylester, liquid crystal polyester etc.)], polyamide resin [such as, fatty polyamide (polyamide 6, polyamide 66, polyamide 610, polymeric amide 11, polymeric amide 12 etc.), aromatic poly amide etc.], polyphenylene oxide resin (polyphenylene oxide, Noryl etc.), polyether ketone resin (polyaryl ether ketone resin or aromatic-polyether ketone resin etc.), polysulfone resin (polysulfones, polyethersulfone etc.), polyimide resin (polyimide, polyamidoimide, polyetherimide etc.), polyphenylene sulfide (polyphenylene sulfide etc.), polyketone sulfide (poly (ketonesulfide)) resin (polyketone sulfide etc.), polybenzimidazole resin (polybenzimidazole etc.) etc.
It should be noted that, thermoplastic resin can be crystalline resin, also can be amorphous resin.
Thermoplastic resin, can be two or more alone or in combination.
Among these thermoplastic resins, as the resin being categorized as engineering plastics (particularly superengineering plastics), can enumerate such as, polyarylester (PAR), liquid crystal polyester (or liquid crystalline polymers, LCP), aromatic poly amide [such as, partially aromatic polyamide (using aromatic dicarboxylic acid composition or the aromatic diamine composition polymeric amide etc. as polymeric composition), Wholly aromatic polyamide etc.], aromatic-polyether ketone resin, polysulfones (PSU), polyethersulfone (PES), polyimide (PI), polyamidoimide (PAI), polyetherimide (PEI), polyphenylene sulfide (PPS), polyketone sulphur compound, polybenzimidazole (PBI) etc.
Wherein, in the present invention, preferred aramid, liquid crystal polyester and aromatic-polyether ketone resin, particularly from the view point of the dispersiveness of fluorine resin, can preferably use aromatic-polyether ketone resin.Below, describe in detail for aromatic poly amide, liquid crystal polyester and aromatic-polyether ketone resin.
(aromatic poly amide)
As aromatic poly amide, can enumerate: the polymeric amide etc. that the composition (such as, dicarboxylic acid component) of at least one party is aromatic component in as the diamine component of polymeric composition and dicarboxylic acid component.Such aromatic poly amide, can be Wholly aromatic polyamide [such as, aromatic diamine composition (composition described later etc.) and aromatic dicarboxylic acid composition (composition described later etc.) are as the polymeric amide of polymeric composition], can be partially aromatic polyamide [such as, in diamine component and dicarboxylic acid component, the composition of a side (such as, aromatic dicarboxylic acid composition) for comprising the polymeric amide of aromatic component], especially also preferably can use partially aromatic polyamide.
As the diamine component forming aromatic poly amide, can enumerate such as: aliphatie diamine composition [alkyl diamine (such as, the C such as quadrol, propylene diamine, butanediamine, hexanediamine, making methylpentamethylenediamine diamine, 2-methyl-prop diamines, 3-methyl-prop diamines, octamethylenediamine, nonamethylene diamine, decamethylene diamine, dodecyl diamines
2-14alkyl diamine etc.) etc.], alicyclic diamine composition [such as, the diamino C such as 1,3-diamino-cyclohexane, Isosorbide-5-Nitrae-diamino-cyclohexane, 1,2-diamino-cyclohexane
5-8naphthenic hydrocarbon; Two (the amino C such as 1,3-bis-(amino methyl) hexanaphthene, Isosorbide-5-Nitrae-two (amino methyl) hexanaphthene, 1,2-bis-(amino methyl) hexanaphthene
1-4alkyl) C
5-8naphthenic hydrocarbon; 4,4 '-diamino-dicyclohexyl methane, 4,4 '-diamino-3,3 '-dimethyidicyclohexyl-methane, 4, two (the amino C such as 4 '-diaminocyclohexyl propane
5-8cycloalkyl) C
1-4alkane; Isophorone diamine etc.], aromatic diamine composition [such as, phenylenediamine (such as, Ursol D etc.), naphthylene diamine (such as, 1,5-diaminonaphthalene etc.), benzidine (such as, 4,4 '-benzidine), two (aminoalkyl group) aromatic hydrocarbons (such as, benzene dimethylamine etc. two (amino C
1-4alkyl) benzene etc.] etc.Diamine component, can be two or more alone or in combination.
As the dicarboxylic acid component forming aromatic poly amide, can enumerate such as, aliphatic dicarboxylic acid composition (such as, the C such as succsinic acid, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, dodecyl diacid, undecyl diacid
2-20alkyl dicarboxylic aid), alicyclic dicarboxylic acid (such as, 1,4-cyclohexane dicarboxylic acid, 1, the C such as 2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-methylhexahydrophthaacid acid, 4-methylhexahydrophthaacid acid
5-10cycloalkyl dicarboxylic acid etc.), aromatic dicarboxylic acid composition (such as, the C such as phthalic acid, terephthalic acid, m-phthalic acid, naphthalene dicarboxylic acids
6-10aromatic hydrocarbons dicarboxylic acid etc.) etc.These dicarboxylic acid component, can be two or more alone or in combination.
Partially aromatic polyamide representatively comprises dicarboxylic acid component and diamine component [at least comprises aliphatie diamine composition (such as, hexanediamine, nonamethylene diamine etc.) etc. the diamine component of non-aromatic diamine component] as polymeric composition polymeric amide [such as, polyphthalamide (PPA) etc.] etc., wherein, this dicarboxylic acid component comprises aromatic dicarboxylic acid composition (the aromatic dicarboxylic acid composition particularly at least containing terephthalic acid composition).
It should be noted that, in such partially aromatic polyamide, aromatic dicarboxylic acid composition and/or diamine component can be two or more alone or in combination.Such as, with regard to aromatic dicarboxylic acid composition, can by terephthalic acid composition and other aromatic dicarboxylic acid composition (such as, m-phthalic acid composition etc.) combination.In addition, can by aromatic dicarboxylic acid composition and the non-aromatic dicarboxylic acid component combination such as (such as, hexanodioic acid aliphatic dicarboxylic acid composition).Further, when by aromatic dicarboxylic acid composition and non-aromatic dicarboxylic acid component combination, whole relative to dicarboxylic acid component, the ratio of aromatic dicarboxylic acid composition can be such as more than 30 % by mole (such as, 35 ~ 99 % by mole), be preferably more than 40 % by mole (such as, 45 ~ 97 % by mole), more preferably more than 50 % by mole (such as, 60 ~ 95 % by mole).
(liquid crystal polyester)
As liquid crystal polyester (liquid crystalline polymers), can be any materials in Wholly aromatic liquid-crystalline polymkeric substance, half aromatic liquid crystal polymers, can preferably use Wholly aromatic liquid-crystalline polymkeric substance especially.
In addition, as long as liquid crystal polyester at least has liquid crystal polyester unit, also can for having other unit (or key, such as, ether unit, amide units, carbonate unit etc.) liquid crystal polyester (such as, liquid crystal polyester ether, liquid crystal polyesteramide, liquid crystal polyester carbonic ether etc.).
As polymeric composition (the polycondensation composition forming liquid crystal polyester, monomer), can enumerate such as: aromatic hydroxycarboxylic acids composition [such as, hydroxy-benzoic acid (P-hydroxybenzoic acid, m-Salicylic acid, salicylic acid), hydroxynaphthoic acid (such as, 6-Hydroxy-2-naphthoic acid, 5-hydroxy-2-naphthoic acid) etc. hydroxy arene carboxylic acid, hydroxy phenyl phenylformic acid (such as, 4 '-hydroxy phenyl-4 benzoic acid, 3 '-hydroxy phenyl-4 benzoic acid) etc.], aromatic dicarboxylic acid composition [such as, benzene dicarboxylic acid (such as, terephthalic acid, m-phthalic acid etc.), naphthalene dicarboxylic acids (such as, 2,6-naphthalene dicarboxylic acids, Isosorbide-5-Nitrae-naphthalene dicarboxylic acids etc.), dicarboxylate biphenyl (such as, 4,4 '-dicarboxyl benzene etc.), diphenyl ether dicarboxylic acid (such as, diphenyl ether-4,4 '-dicarboxylic acid etc.) etc.], aromatic diol composition [such as, Benzenediol (such as, quinhydrones etc.), dihydroxy naphthlene (such as, 2,6-dihydroxy naphthlene etc.), dihydroxybiphenyl (such as, 4,4 '-xenol etc.), dihydroxydiphenyl ether (such as, 4,4 '-dihydroxydiphenyl ether) etc.], aromatic hydroxy amine component [such as, amino-phenol (such as, p-aminophenol etc.), amino-naphthol (such as, 4-amino-1-naphthols etc.), hydroxy amino biphenyl (such as, 4-amino-4 '-xenol etc.) etc.], aromatic diamine composition [such as, phenylenediamine (such as, Ursol D etc.), naphthylene diamine (such as, 1,5-diaminonaphthalene etc.), benzidine (such as, 4,4 '-benzidine) etc.], aromatic aminocarboxylic acids composition [such as, benzaminic acid (such as, para-amino benzoic acid etc.), amino naphthalenes formic acid (such as, 6-amino naphthalenes formic acid etc.) etc.] etc. aromatic component (difunctional aromatic's composition).
Aromatic component also can have substituting group (such as, alkyl, alkoxyl group, halogen atom etc.).In addition, also reactive derivatives is comprised [such as in aromatic component, hydroxyl is substituted by the compound of acyloxy, carboxyl substituted be ester group (such as, alkyl-carbonyl, aryloxycarbonyl etc.) or acid halide group is (such as, formyl chloro) compound, amino is substituted by the compound of amido) etc.].
These aromatic component, can be two or more alone or in combination.
In addition, polymeric composition at least comprises these aromatic component usually, can also comprise nonaromatic component { such as, aliphatic diol composition (such as, the C such as ethylene glycol, BDO
2-10alkyl diol), polyester component [such as, comprises poly-aromatic acid alkane diol ester (such as, the poly-C such as polyethylene terephthalate, polybutylene terephthalate, PEN
6-10aromatic acid C
2-4alkane diol ester) etc. the polyester component of aliphatics skeleton] etc., more than trifunctional composition [such as, aromatic hydroxy dicarboxylic acid component (such as, hydroxyl isophthalic acid, hydroxyl naphthalene dicarboxylic acids etc.) etc.].These compositions, can be two or more alone or in combination.
Comprise at least using aromatic hydroxycarboxylic acids composition as the liquid crystal polyester of polymeric composition as concrete liquid crystal polyester, this aromatic hydroxycarboxylic acids composition is such as: (i) aromatic hydroxycarboxylic acids composition (such as, hydroxy-benzoic acid composition etc.) and aromatic dicarboxylic acid composition is (such as, benzene dicarboxylic acid composition, naphthalene dicarboxylic acids etc.) and the polycondensate of at least a kind of composition selected from aromatic diol composition (such as, dihydroxybiphenyl etc.), aromatic hydroxy amine and aromatic diamine; (ii) polycondensate of aromatic hydroxycarboxylic acids composition [such as, hydroxy-benzoic acid composition and other aromatic hydroxycarboxylic acids composition (such as, hydroxynaphthoic acid composition etc.)] of more than 2; (iii) aromatic hydroxycarboxylic acids composition (such as, hydroxy-benzoic acid composition) and aromatic dicarboxylic acid composition is (such as, benzene dicarboxylic acid composition, naphthalene dicarboxylic acids etc.) and the polycondensate etc. of polyester component (such as, aromatic acid alkane diol ester (polyalkylenearylate) etc.).
Liquid crystal polyester can be at least using the liquid crystal polyester of hydroxy-benzoic acid composition as polymeric composition usually, can be using hydroxy-benzoic acid composition and other polymeric composition liquid crystal polyester as polymeric composition especially.Comprising other polymeric composition like this as in the liquid crystal polyester of polymeric composition, hydroxy-benzoic acid composition (the 4-HBA composition etc.) ratio whole relative to polymeric composition such as can be 10 ~ 95 % by mole, be preferably 20 ~ 90 % by mole, more preferably about 30 ~ 80 % by mole.
(aromatic-polyether ketone resin)
With regard to aromatic-polyether ketone resin (polyaryl ether ketone resin), usually, the situation containing the repeating unit comprising arylidene and ether [-O-] and carbonyl [-C (=O)-] is more.As such resin, be not particularly limited, can comprise such as, the repeating unit shown arbitrarily in following formula (a1) ~ (a5).
[-Ar-O-Ar-C(＝O)-](a1)
[-Ar-O-Ar-C(＝O)-Ar-C(＝O)-](a2)
[-Ar-O-Ar-O-Ar-C(＝O)-](a3)
[-Ar-O-Ar-C(＝O)-Ar-O-Ar-C(＝O)-Ar-C(＝O)-](a4)
[-Ar-O-Ar-O-Ar-C(＝O)-Ar-C(＝O)-](a5)
(in formula, Ar represents to have arbitrarily substituent divalent aromatic hydrocarbon cyclic group)
As the divalent aromatic hydrocarbon cyclic group shown in Ar, can illustrate such as: phenylene (adjacent, or to phenylene etc.); The C such as naphthylidene
6-10arylidene; The Asia such as biphenylene (2,2 '-biphenylene, 3,3 '-biphenylene, 4,4 '-biphenylene etc.) connection C
6-10aryl; Adjacent, or to sub-three C such as sub-terphenyl
6-10aryl etc.These aromatic hydrocarbon cyclic groups, also can have substituting group such as, halogen atom, the alkyl (C of the straight-chain such as methyl or branched
1-4alkyl etc.), alkylhalide group, hydroxyl, the alkoxyl group (C of the straight-chain such as methoxyl group or branched
1-4alkoxyl group etc.), sulfydryl, alkyl sulfenyl, carboxyl, sulfo group, amino, N-substituted-amino, cyano group etc.It should be noted that, in repeating unit (a1) ~ (a5), the kind of each Ar can be identical mutually, also can be different.
Preferred Ar is phenylene (such as, to phenylene), biphenylene (such as, 4,4 '-biphenylene).
As the resin with repeating unit (a1), polyetherketone (such as, Victrex company manufactures " PEEK-HT ") etc. can be illustrated.As the resin with repeating unit (a2), PEKK (such as, Arkema+OxfordPerformanceMaterial company manufactures " PEKK ") etc. can be illustrated.As the resin with repeating unit (a3), polyether-ether-ketone can be illustrated (such as, Victrex company manufactures " VICTREXPEEK ", Evonik company manufactures " Vestakeep (registered trademark) ", Daicel-Evonik company manufactures " Vestakeep-J ", SolvayAdvancedPolymers company manufactures " Ketaspire (registered trademark) "), polyether-diphenyl-ether-phenyl-ketone-phenyl (such as, SolvayAdvancedPolymers company manufacture " Kadel (registered trademark) ") etc.As the resin with repeating unit (a4), polyetherketoneetherketoneketone (such as, Victrex company manufactures " VICTREXST ") etc. can be illustrated.As the resin with repeating unit (a5), polyether ether ketone ketone etc. can be illustrated.
In the repeating unit comprising arylidene and ether group and carbonyl, the ratio of ether section (E) and ketone section (K), such as the former/the latter (E/K)=0.5/1 ~ 2/1, be preferably about 1/1 ~ 2/1.Ether section gives molecular chain flexibility, and ketone section gives molecular chain rigidity, therefore there is following tendency: more multiple crystallization speed is faster for ether section, and the degree of crystallinity that finally can reach is higher; Ketone Duan Yue is many, second-order transition temperature and fusing point higher.
Among aromatic-polyether ketone resin, preferably there is arbitrary aromatic-polyether ketone resin in repeating unit (a1) ~ (a3), particularly from the view point of balanced excellent between higher glass transition temperature and fusing point and very fast crystallization rate, preferably there is the aromatic-polyether ketone resin (such as, polyether-ether-ketone) of repeating unit (a3).
It should be noted that, with regard to aromatic-polyether ketone resin, commercially available product as described above can be utilized, also can utilize by conventional method (such as, by the method for aromatic diol composition and the condensation of aromatic dihalide compound composition, aromatics list halogenide single methanol composition is utilized the method for nucleophilic substitution reaction from the method etc. of condensation) material that synthesizes.
As aromatic diol composition, dihydroxy-benzene (quinhydrones etc.), dihydroxy benaophenonel (4,4'-Dihydroxybenzophenone etc.) etc. can be illustrated.As aromatic dihalide compound composition, dihalobenzophenone (4,4 '-difluoro benzophenone, 4,4 '-dichloro benzophenone etc.) etc. can be illustrated.As aromatics list halogenide single methanol composition, halogenated hydroxyl benzophenone (the fluoro-4 '-dihydroxy benaophenonel of 4-etc.) etc. can be illustrated.
Condensation reaction can be carried out under the existence of alkali and/or solvent.As alkali, an alkali metal salt can be illustrated, the alkaline carbonates etc. such as such as (anhydrous) salt of wormwood.As solvent, high boiling solvent can be illustrated, such as sulfobenzide, tetramethylene sulfone etc.Temperature of reaction such as can be 150 ~ 400 DEG C, is preferably about 200 ~ 350 DEG C.
It should be noted that, reaction product such as, can be filtered by conventional separation means, concentrated, crystallization, chromatography etc. carry out separation and purification.In addition, reaction product also can carry out as required washing, dry.As cleaning solvent, water, alcohols (methyl alcohol, ethanol etc.), ketone (acetone etc.), their mixed solvent etc. can be illustrated.Further, with regard to the reaction product of solid-state shape, can fragmentation be carried out to adjust granularity, also can carry out classification.
From the viewpoint of adjustment crystallized temperature etc., with regard to the end group (halogen atom etc.) of reaction product, can modify with such as alkali sulfonate groups (lithium sulfonate groups, sodium sulfonate groups, potassium sulfonate groups etc.) etc.
The number-average molecular weight of thermoplastic resin is not particularly limited, such as, can be, in gel permeation chromatography (GPC), with polystyrene conversion for 5, more than 000 (such as, 5,000 ~ 1,000,000), 8 are preferably, more than 000 (such as, 10,000 ~ 500,000), more preferably 15, more than 000 (such as, 20,000 ~ 100,000).
The second-order transition temperature (Tg) of thermoplastic resin or fusing point, be not particularly limited, and can select according to the kind of resin is suitable.Such as, when thermoplastic resin is the resin of the such high heat resistance of engineering plastics (particularly superengineering plastics), second-order transition temperature can be more than 60 DEG C (such as, 65 ~ 250 DEG C), be preferably more than 70 DEG C (such as, 85 ~ 230 DEG C), more preferably more than 80 DEG C (such as, 85 ~ 200 DEG C), can be more than 100 DEG C especially.Particularly the second-order transition temperature (Tg) of aromatic-polyether ketone resin such as can be more than 100 DEG C, is preferably 120 ~ 200 DEG C, more preferably about 140 ~ 180 DEG C.
In addition, when thermoplastic resin is resin (crystalline resin) of the such high heat resistance of engineering plastics (particularly superengineering plastics), fusing point can from more than 150 DEG C (such as, 180 ~ 450 DEG C) scope select, also more than 200 DEG C can be preferably (such as, 230 ~ 430 DEG C), more preferably more than 250 DEG C (such as, 270 ~ 400 DEG C).The particularly fusing point of aromatic-polyether ketone resin, such as, can be more than 300 DEG C, is preferably 310 ~ 400 DEG C, more preferably about 320 ~ 380 DEG C.
Second-order transition temperature and fusing point, such as, can pass through differential scanning calorimetric analysis (DSC) and measure.
It should be noted that, the melt viscosity of thermoplastic resin is not particularly limited, and disperses fluorine resin well and to obtain the photostabilization effect of substantially improving such, there is the situation preferably with appropriate viscosity from the viewpoint of efficiency.
From the viewpoint, such as, by aromatic-polyether ketone resin in 400 DEG C, velocity of shear 60s
-1melt viscosity when being set to Va, Va can be such as 50 ~ 4000Pas, is preferably 100 ~ 3000Pas, more preferably 150 ~ 2500Pas, particularly about 200 ~ 2000Pas.Melt viscosity can use conventional device, and such as, capillary rheometer measures.
In addition, from the viewpoint of dispersiveness, there is the situation of the melt viscosity ratio preferably between appropriateness adjustment thermoplastic resin and fluorine resin.Such as, combination two kinds of compositions can be selected, and by fluorine resin at specified temperature [temperature (such as, 390 DEG C) such as, in forcing machine during the melting mixing such as temperature cylinder], velocity of shear 60s
-1melt viscosity when being set to Vb, thus make the melt viscosity ratio of thermoplastic resin and fluorine resin as being Va/Vb=0.05/1 ~ 10/1, be preferably 0.1/1 ~ 8/1, more preferably 0.2/1 ~ 7/1, especially 0.3/1 ~ 6/1 (such as, 0.3/1 ~ 5/1) left and right.
Relative to thermoplastic resin 100 weight part, the usage ratio (adding proportion) of additive of the present invention (light fastness enhancer) such as can from 0.1 ~ 300 weight part (such as, 0.5 ~ 200 weight part) left and right scope select, it can be 1 ~ 150 weight part, be preferably 3 ~ 100 weight parts, more preferably 5 ~ 90 weight parts, and be preferably 7 ~ 80 weight parts (such as, 10 ~ 70 weight parts) left and right.
Particularly additive of the present invention, even if also can obtain because ratio is lower improving sunproof effect fully, therefore relative to thermoplastic resin 100 weight part, the usage ratio (adding proportion) of light fastness enhancer can be such as below 20 weight parts (such as, 1 ~ 18 weight part), be preferably below 15 weight parts (such as, 2 ~ 12 weight parts), more preferably (such as, 3 ~ 8 weight parts) below 10 weight parts left and right.
On the other hand, because light fastness enhancer of the present invention is arborescens, even if therefore ratio is higher, does not produce yet and ooze out, can efficiency to be improved well sunproof effect.Therefore, inferior in preferred situation of the characteristic being derived from fluorine resin being given energetically thermoplastic resin, relative to thermoplastic resin 100 weight part, the usage ratio of light fastness enhancer can be more than 20 weight parts (such as, 20 ~ 200 weight parts), be preferably more than 25 weight parts (such as, 27 ~ 150 weight parts), more preferably more than 30 weight parts (such as, 35 ~ 100 weight parts) left and right.
It should be noted that, relative to the total amount of fluorine-free thermoplastic resin and fluorine resin, the volume ratio (volume usage ratio) of fluorine resin (or disperse phase described later) can from 0.1 ~ 95% (such as, 0.3 ~ 90%) scope of left and right is selected, can be such as 0.5 ~ 85% (such as, 0.7 ~ 80%), be preferably 1 ~ 70% (such as, 1.5 ~ 60%), more preferably 2 ~ 60% (such as, 2.5 ~ 50%), particularly 3 ~ 45% (such as, 4 ~ 40%) left and right.
As mentioned above, by light fastness enhancer of the present invention, can be improved (or impart or showed) sunproof resin (resin combination).The present invention also comprises such resin combination, namely comprises the resin combination of thermoplastic resin (fluorine-free thermoplastic resin) and light fastness enhancer (fluorine resin).
It should be noted that, in such resin combination, the kind of thermoplastic resin, light fastness enhancer (fluorine resin) or its blending ratio, can select from scope same as described above.
As long as in the scope not affecting effect of the present invention, resin combination can comprise other additive as required.As other additive, can illustrate such as, stablizer (thermo-stabilizer, photostabilizer etc.), filler [such as, the mineral filler such as glass fibre, glass powder, carbon fiber, carbon dust, carbon nanotube, metal oxide (aluminum oxide, zinc oxide etc.), metal nitride (aluminium nitride, boron nitride etc.)], softening agent, lubricant, tinting material etc.These other additives, can individually use or combine more than two kinds uses.
Resin combination preferably can comprise filler (or strengthening material) especially.
Filler (or weighting agent) can be the arbitrary shape such as threadiness, needle-like (whisker), particle shape, tabular, particularly preferably threadiness or needle-like.
As fibrous filler, can enumerate such as, inorganic fibre (such as, glass fibre, carbon fiber, boron fibre, activated carbon fiber, manosil AS fiber, sapphire whisker, silicon carbide fiber, steel fiber, potassium titanate fiber etc.), organic fibre (such as, aramid fiber, liquid crystalline polyester fiber etc.).As needle-like weighting agent, can enumerate such as, silicate (wollastonite etc.), potassium titanate crystal whisker, aluminium borate whisker, alumina whisker, calcium carbonate crystal whisker etc.Filler can be two or more alone or in combination.
Wherein, from the sunproof viewpoint of the combination with fluorine-free thermoplastic resin (and fluorine resin), can preferably use glass fibre, needle-like weighting agent etc.In addition, from the viewpoint of the rigidity or the intensity that keep thin-walled portion, also these fillers preferred.
It should be noted that, for improving the object such as dispersiveness of filler relative to thermoplastic resin, surface treatment can be carried out with surface treatment agent to filler.As surface treatment agent, can enumerate such as, [such as, coupling agent (such as organic surface treatment agent, silane coupling agent, titanium coupling agent etc.), resin (such as, acrylic resin, carbamate resins, epoxy resin etc.) etc.] etc.Surface treatment agent can be two or more alone or in combination.
Relative to thermoplastic resin 100 weight part, the ratio of other additive can according to selections such as its kinds, the ratio of such as filler can from 0.5 ~ 200 weight part (such as, 0.7 ~ 150 weight part) left and right scope select, also can be 1 ~ 100 weight part, about being preferably 3 ~ 80 weight parts, more preferably 5 ~ 60 weight parts, particularly 10 ~ 50 weight parts.
In addition, relative to total amount 100 weight part of thermoplastic resin and fluorine resin, the ratio of filler can from 0.3 ~ 150 weight part (such as, 0.5 ~ 120 weight part) left and right scope select, also can be 1 ~ 100 weight part, be preferably 2 ~ 80 weight parts, more preferably 3 ~ 60 weight parts, particularly 5 ~ 50 weight parts (such as, 8 ~ 40 weight parts) left and right.
The melt viscosity of resin combination can be selected, such as, when thermoplastic resin is aromatic-polyether ketone resin, in temperature 400 DEG C, velocity of shear 60s according to the kind of thermoplastic resin is suitable
-1melt viscosity can be such as 50 ~ 4000Pas, be preferably 100 ~ 3000Pas, and be preferably about 150 ~ 2500Pas.
Resin combination can also have phase separation structure.When having such phase separation structure, any one in thermoplastic resin and light fastness enhancer can form external phase or disperse phase.It should be noted that, determine that forming external phase still forms disperse phase according to the kind of thermoplastic resin or the adding proportion (blending ratio) of light fastness enhancer etc., but usually can be formed (or external phase comprises thermoplastic resin) external phase by thermoplastic resin, form (or disperse phase comprises light fastness enhancer (fluorine resin)) disperse phase by light fastness enhancer (fluorine resin).Disperse phase can be isotropy shape, also can be Anisotropic shapes.
The median size of disperse phase can be such as less than 300 μm (such as, 0.01 ~ 250 μm), be preferably less than 200 μm (such as, 0.03 ~ 150 μm), more preferably less than 100 μm (such as, 0.05 ~ 70 μm).Particularly according to the kind of resin, in order to efficiency is improved sunproof effect well, there is the situation of the median size (that is, making its differential fall apart) preferably reducing disperse phase.Under these circumstances, the median size of disperse phase can from less than 30 μm (such as, less than 10 μm) scope select: can be less than 5 μm, such as, less than 3 μm (such as, less than 2 μm), be preferably less than 1 μm (such as, less than 0.7 μm), more preferably less than 0.6 μm (such as, about 0.01 ~ 0.5 μm); Also can be less than 0.5 μm, be preferably less than 0.4 μm, more preferably less than 0.3 μm.When such median size is below 3 μm, the maximum particle diameter of disperse phase such as can be less than 4 μm, is preferably less than 3 μm (such as, less than 2 μm), more preferably less than 1 μm (such as, less than 0.8 μm).
In addition, disperse phase (such as, fluorine resin) average interparticle distance be less than 200 μm (such as, less than 150 μm, be preferably less than 100 μm), usually can select from the scope of less than 30 μm (such as, less than 20 μm) left and right, such as, can be less than 10 μm (such as, less than 7 μm), be preferably less than 5 μm (such as, 0.01 ~ 4 μm), more preferably less than 3 μm (such as, 0.1 ~ 2.5 μm), particularly less than 2 μm (such as, 0.2 ~ 1.5 μm).
There is particle diameter or the spacing of particle (and volume ratio) by adjusting disperse phase as mentioned above, obtaining more efficiency and improving the situation of sunproof effect well.
It should be noted that, the particle diameter of disperse phase or spacing of particle [and ratio (part by weight and/or volume ratio] can by following mensuration: utilize conventional device [transmission electron microscope (TEM), scanning electron microscope (SEM), laser microscope, atomic force microscope (AFM) etc.] to carry out microscopic examination to the sheet formed by resin combination, carry out binary conversion treatment etc. with optical assay device to the image obtained.
The manufacture method of resin combination (or the addition means of light fastness enhancer or using method) is not particularly limited, and can manufacture by thermoplastic resin and light fastness enhancer (fluorine resin) being carried out mix (added by light fastness enhancer or be mixed in thermoplastic resin).It should be noted that, light fastness enhancer can be described above, carries out mixing and make it be scattered in thermoplastic resin.Specifically, resin combination can be prepared by each composition is carried out melt kneading usually.More specifically, following situation is more: each composition is carried out ready-mixed through mixing machine (roller machine, V-Mixer, Henschel mixing tank, nauta mixer (nautamixer), ribbon mixer, mechanochemistry device, extrude mixing machine etc.) as required, then melt kneading (or melting mixing) is carried out with various kneader (such as, mixing roll, singe screw or twin screw extruder etc.).Mixing or to mediate temperature (melt kneading temperature) be at least can the temperature temperature of molten thermoplastic resin and fluorine resin (particularly can) of molten thermoplastic resin, different according to the kind of resin, such as can from more than 100 DEG C (such as, 130 ~ 500 DEG C), be preferably more than 150 DEG C (such as, 180 ~ 450 DEG C), the scope of more preferably more than 200 DEG C (such as, 250 ~ 400 DEG C) is selected.Particularly when thermoplastic resin is aromatic-polyether ketone resin, mixing temperature such as can be 300 ~ 450 DEG C, is preferably about 350 ~ 400 DEG C.Stirring velocity (speed of rotation) can be such as 150 ~ 500rpm, is preferably 200 ~ 400rpm (such as, 250 ~ 350rpm) left and right.Molten mixture (melt kneading thing), can carry out granulation by conventional granulation means (tablets press etc.).
Obtain resin combination as mentioned above.The method that resin combination can pass through to commonly use is shaping and use.Therefore, in the present invention, also comprise the formed body formed by described resin combination.The shape of formed body, such as, can be membranaceous or the two-dimensional shapes such as sheet, also can be bar-shaped, the 3D shape etc. such as tubulose, tabular.
Formed body by conventional method, such as, extrusion moulding, injection moulding, the formation such as stamping.In injection moulding etc., temperature cylinder can be selected from the scope equal with melt mix temperature.
Embodiment
Below, based on embodiment, the present invention is further illustrated, but the present invention is not limited to these embodiments.It should be noted that, as described below to the evaluation method of the various raw materials used, various physical property.
[raw material]
(fluorine-free thermoplastic resin)
PEEK (polyether-ether-ketone): Daicel-Evonik (strain) manufactures, Vestakeep-JZV7403
PPA (partially aromatic polyamide): Daicel-Evonik (strain) manufactures, VESTAMIDHTplusM1000
LCP (liquid crystal polyester): Polyplastics (strain) manufactures, VectraA130 (glass fibre 30% is containing product)
(fluorine resin)
Hexafluoropropylene (HFP)/tetrafluoroethylene (TFE) analog copolymer (composition weight ratio: tetrafluoroethylene/hexafluoropropylene/perfluor (propyl vinyl ether)=87.5/11.5/1.0, MFR:27g/10 minute), hereinafter referred to as " FEP ".
Tetrafluoroethylene-perfluoroalkyl vinyl ether analog copolymer (composition weight ratio: tetrafluoroethylene/perfluoro (propyl vinyl ether)=94.5/5.5, MFR; 23g/10 minute), hereinafter referred to as " PFA ".
Tetrafluoroethylene: trade(brand)name " KTH-645 ", (strain) Xi Duo village manufactures, hereinafter referred to as " PTFE ".
(antioxidant)
Trade(brand)name " SUMILIZERGA-80 ", Sumitomo Chemical (strain) manufactures
(photostabilizer)
Trade(brand)name " TINUVIN234 ", BASF AG manufactures
[light fastness test]
Use metal halide formula light fastness test machine (DaiplaWintes manufactures SUPERWINMINISWM-03FS), with 200 hours, 120 DEG C, exposure intensity 160W/m
2under the condition of (intensity at 300 ~ 400nm place), rayed is carried out to JIS test film.
[conservation rate of the conservation rate of tensile strength and tension fracture strain]
In the front and back of light fastness test, according to JISK7113, tensile strength and tension fracture strain are measured.And, calculate these velocity of variation by following formula respectively from these measured values.
Conservation rate=[the B of tensile strength
1/ A
1] × 100 (%)
(in formula, A
1represent the tensile strength of the resin combination before light fastness test, B
1represent the tensile strength of the resin combination after light fastness test.)
Conservation rate=[the B of tension fracture strain
2/ A
2] × 100 (%)
(in formula, A
2represent the tension fracture strain of the resin combination before light fastness test, B
2represent the tension fracture strain of the resin combination after light fastness test.)
[extrudability]
By thickening in forcing machine and the material that can not obtain granular resin combination (resin particle) be evaluated as ×, not such material is evaluated as zero.
[median size of disperse phase (fluorine resin) and average interparticle distance]
By from resin combination with the temperature of regulation (PEEK in 380 DEG C, PPA in 340 DEG C, LCP is in 350 DEG C) carry out the hot-forming compressed tablet obtained, (Leica company manufactures to be fixed on ultramicrotome, ULTRACUTS) sample holder, be cooled to-80 DEG C with liquid nitrogen by chamber, cut the thin section of thickness 90nm.By the platinum loop being attached with 20% ethanolic soln, the thin section obtained is reclaimed, make it be attached to sheet screen cloth made of copper (thing of should consulting and deliberating company manufactures, 200A).(Hitachi manufactures Zuo Suo company and manufactures to use transmission electron microscope, H7100FA), observation is attached to the thin section of sheet screen cloth made of copper and makes negative film, by this negative film, by scanner, (EPSON company manufactures, GT-9400UF) electronic image is carried out, use optical assay device (Nireco company manufactures, LUZEXAP) to carry out the binary conversion treatment of electronic image, calculate median size and the average interparticle distance of disperse phase (fluorine resin).
(embodiment 1 ~ 7 and comparative example 1 ~ 2)
After composition ready-mixed shown in showing with the mixing ratio (part by weight, volume ratio) shown in following table (embodiment 1 ~ 7 and comparative example 1) or direct (comparative example 2), knock down the main hopper of two screw kneading extruder, under the condition of temperature cylinder 370 DEG C, screw speed 300rpm, carry out melt kneading and carry out extruding obtaining resin combination (the extrudability material being evaluated as zero is granular resin combination).
Then, the particle of the resin combination obtained is knocked down the injection moulding machine (temperature cylinder 380 DEG C) that JIS test film die for manufacturing (die temperature 200 DEG C) is housed and carry out injection moulding, manufacture various JIS test film, various characteristic is measured.It should be noted that, owing to not obtaining granular resin combination in comparative example 1, so there is no the mensuration of carrying out various characteristic.
(embodiment 8 and comparative example 3)
After composition ready-mixed shown in showing with the mixing ratio (part by weight, volume ratio) shown in following table (embodiment 8) or direct (comparative example 3), knock down the main hopper of two screw kneading extruder, under the condition of temperature cylinder 340 DEG C, screw speed 300rpm, carry out melt kneading and carry out extruding obtaining resin combination.
Then, the particle of the resin combination obtained is knocked down the injection moulding machine (temperature cylinder 340 DEG C) being provided with JIS test film die for manufacturing (die temperature 140 DEG C) and carry out injection moulding, manufacture various JIS test film, various characteristic is measured.
(embodiment 9 and comparative example 4)
After composition ready-mixed shown in showing with the mixing ratio (part by weight, volume ratio) shown in following table (embodiment 9) or direct (comparative example 4), knock down the main hopper of two screw kneading extruder, under the condition of temperature cylinder 370 DEG C, screw speed 300rpm, carry out melt kneading and carry out extruding obtaining resin combination.
Then, the particle of the resin combination obtained is knocked down the injection moulding machine (temperature cylinder 350 DEG C) that JIS test film die for manufacturing (die temperature 80 DEG C) is housed and carry out injection moulding, manufacture various JIS test film, various characteristic is measured.
Result is shown in table.It should be noted that, the volume ratio in table, is the volume ratio of the total amount relative to fluorine-free thermoplastic resin (PEEK, PPA, LCP) and fluorine resin (FEP, PFA or PTFE).
[table 1]
[table 2]
Known from the result of table: by adding fluorine resin to fluorine-free thermoplastic resin (PEEK, PPA, LCP), to improve photostabilization.
Industrial applicibility
Additive of the present invention is effective as the sunproof additive for improving or improve fluorine-free thermoplastic resin.And, additive of the present invention, even if the melting mixing process under high temperature, also can keep improving sunproof effect, therefore the photostabilization improving or improve superengineering plastics (such as, aromatic poly amide, liquid crystal polyester, aromatics gather aryl ketones resin) is particularly preferred for.
In addition, improve through such additive of the present invention or improve sunproof fluorine-free thermoplastic resin (resin combination of fluorine-free thermoplastic resin and light fastness enhancer), various uses can be used according to the kind of resin, can preferably as such as: the utilizations such as the member of formation of household electrical appliance, office automation (OA) equipment, mobile equipment etc.Particularly, the situation also excellent due to such resin combination mechanical characteristics is more, therefore the also preferred slim switch etc. as smart mobile phone, PC (notebook type, panel computer type etc.), E-book reader, digital camera etc.
Claims (10)
1. a light fastness enhancer, it is the sunproof additive for improving or improve fluorine-free thermoplastic resin, and it comprises:
Fluorine resin.
2. light fastness enhancer according to claim 1, wherein, fluorine resin is using the fluorine resin of tetrafluoroethylene as polymeric composition.
3. light fastness enhancer according to claim 1 and 2, wherein, fluorine resin is thermoplastic fluorocarbon resin.
4. the light fastness enhancer according to any one of claims 1 to 3, wherein fluorine resin is TFE copolymer.
5. the light fastness enhancer according to any one of Claims 1 to 4, wherein, fluorine resin is be selected from least a kind in the multipolymer of tetrafluoroethylene and other fluorinated olefin, tetrafluoroethylene and the multipolymer of fluorinated vinyl ether and the multipolymer of tetrafluoroethylene and other fluorinated olefin and fluorinated vinyl ether.
6. the light fastness enhancer according to any one of Claims 1 to 5, wherein, fluorine resin is be selected from least a kind in the multipolymer of tetrafluoroethylene and other perfluoroolefine, tetrafluoroethylene and the multipolymer of perfluor (alkyl vinyl ether) and the multipolymer of tetrafluoroethylene and other perfluoroolefine and perfluor (alkyl vinyl ether).
7. the light fastness enhancer according to any one of claim 1 ~ 6, wherein, fluorine-free thermoplastic resin is superengineering plastics.
8. the light fastness enhancer according to any one of claim 1 ~ 7, wherein, fluorine-free thermoplastic resin is be selected from least a kind in aromatic poly amide, liquid crystal polyester and aromatic-polyether ketone resin.
9. the light fastness enhancer according to any one of claim 1 ~ 8, wherein, fluorine-free thermoplastic resin is polyether-ether-ketone.
10. improve a sunproof method for fluorine-free thermoplastic resin, it comprises:
Light fastness enhancer according to any one of claim 1 ~ 9 is added into fluorine-free thermoplastic resin.
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| JP2013-086720 | 2013-04-17 | ||
| PCT/JP2013/078189 WO2014171028A1 (en) | 2013-04-17 | 2013-10-17 | Light-resistance improver |
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| EP (1) | EP2987832B1 (en) |
| JP (1) | JP6211601B2 (en) |
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| JP6958546B2 (en) | 2016-04-28 | 2021-11-02 | Ａｇｃ株式会社 | Fluorine-containing copolymer composition, its production method, and molded article |
| EP4023438A4 (en) * | 2019-08-27 | 2023-09-13 | Toray Industries, Inc. | LIQUID CRYSTALLINE POLYESTER RESIN COMPOSITION, LAMINATE, LIQUID CRYSTALLINE POLYESTER RESIN FILM AND METHOD FOR THE PRODUCTION THEREOF |
| FR3127496B1 (en) * | 2021-09-28 | 2025-01-17 | Arkema France | Powder based on polyaryletherketone(s) for the manufacture of ductile objects. |
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- 2013-10-17 KR KR1020157032455A patent/KR102117275B1/en active Active
- 2013-10-17 EP EP13882347.1A patent/EP2987832B1/en active Active
- 2013-10-17 JP JP2015512276A patent/JP6211601B2/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115210315A (en) * | 2020-03-10 | 2022-10-18 | 大金工业株式会社 | Resin composition, molded article, and method for producing molded article |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2987832B1 (en) | 2019-02-06 |
| JPWO2014171028A1 (en) | 2017-02-16 |
| US10246586B2 (en) | 2019-04-02 |
| EP2987832A1 (en) | 2016-02-24 |
| WO2014171028A1 (en) | 2014-10-23 |
| US20160046806A1 (en) | 2016-02-18 |
| JP6211601B2 (en) | 2017-10-11 |
| EP2987832A4 (en) | 2017-03-29 |
| CN105324438B (en) | 2020-11-06 |
| KR20150143691A (en) | 2015-12-23 |
| KR102117275B1 (en) | 2020-06-01 |
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